Process for preparing hydroxyphenyl ethers

Abstract

A process for preparing hydroxyphenyl ethers by oxidizing phenyl ethers with hydrogen peroxide in the presence of a ketone or with a ketone peroxide.

What is claimed is: 
     
       1. A process for preparing a hydroxyphenyl ether having the formula: ##STR10## wherein R represents an alkyl radical or a phenyl radical and R' represents a hydrogen atom or an alkyl radical, which comprises oxidizing a phenyl ether having the formula: ##STR11## wherein R and R' have the same meanings as above, with hydrogen peroxide in the presence of a ketone, or with a ketone peroxide, at a temperature of 20° to 250° C. in the presence of a catalyst selected from the group consisting of an activated clay, a boric acid or a boric acid derivative, the amount of catalyst being more than 0.001 weight percent of said phenyl ether, said ketone being selected from the group consisting of (i) through (iii) following: i. a ketone having from 3 to 20 carbon atoms and represented by the following formula:   R.sub.1 -- CO -- R.sub.2        wherein R 1  and R 2  may be the same or different and each represents a straight or branched alkyl group of 1 - 18 carbon atoms or phenyl group, and either R 1  or R 2  may be an aliphatic group having an unsaturated bond;   ii. a diketone having from 3 to 20 carbon atoms and represented by the following formula: ##STR12##  wherein n is an integer of from 0 to 16, inclusive, and R 1  and R 2  have the same meanings as above;   iii. a cycloketone having the following formula: ##STR13##  wherein n 1  represents an integer of from 4 to 11, inclusive, l + m represents an integer of from 3 to 10, inclusive, and R 1  has the same meaning as above; and said ketone peroxide being obtained by reaction of hydrogen peroxide and a ketone selected from the group of said (i) to (iii) or derived from a secondary alcohol selected from the group consisting of a secondary alcohol having the following formula:   iv. a secondary alcohol having from 3 to 20 carbon atoms and represented by the following formula: ##STR14##  wherein R 1  and R 2  have the same meanings as above; v. a di-secondary alcohol having from 3 to 20 carbon atoms and represented by the following formula: ##STR15##  wherein R 1 , R 2  and n have the same meanings as above; and vi. a cycloalcohol having the following formula: ##STR16##  wherein R 1 , n 1 , l and m have the same meanings as above.   
     
     
       2. The process for preparing a hydroxyphenyl ether as claimed in claim 1 which comprises oxidizing the phenyl ether with hydrogen peroxide in the presence of a ketone. 
     
     
       3. The process for preparing a hydroxyphenyl ether as claimed in claim 1 which comprises oxidizing the phenyl ether with a ketone peroxide. 
     
     
       4. The process as claimed in claim 2 in which the ketone is a ketone selected from the group consisting of a saturated aliphatic monoketone having 3 - 15 carbon atoms, a saturated alicyclic monoketone having 5 - 12 carbon atoms and an aromatic ketone, each of which is unsubstituted. 
     
     
       5. The process as claimed in claim 2 in which the oxidation of the phenyl ether is conducted by using hydrogen peroxide in a 0.005 - 0.5 molar ratio to the phenyl ether, and the ketone in a 0.005 - 20 molar ratio to hydrogen peroxide. 
     
     
       6. The process as claimed in claim 1 in which the oxidation of the phenyl ether is conducted at a temperature of 80° - 200° C. 
     
     
       7. The process as claimed in claim 3 in which the ketone peroxide is derived from a ketone selected from the group consisting of a saturated aliphatic monoketone having 3 - 15 carbon atoms, a saturated alicyclic monoketone having 5 - 12 carbon atoms and an aromatic monoketone. 
     
     
       8. The process as claimed in claim 3 in which the ketone peroxide is derived by the autoxidation of a secondary alcohol selected from the group consisting of a saturated monoalcohol having 3 - 15 carbon atoms, a saturated alicyclic monoalcohol having 5 - 12 carbon atoms and an aromatic monoalcohol. 
     
     
       9. The process as claimed in claim 3 in which the oxidation of a phenyl ether is conducted by using a ketone peroxide in an amount of 0.005 - 1.00 m. atom number of active oxygen contained in the ketone peroxide per m. mole number of phenyl ether. 
     
     
       10. The process as claimed in claim 3 in which the oxidation of the phenyl ether is conducted at a temperature of 80° - 200° C. 
     
     
       11. The process as claimed in claim 1, wherein the catalyst is an activated clay. 
     
     
       12. The process as claimed in claim 1, wherein the catalyst is orthoboric acid. 
     
     
       13. The process as claimed in claim 1, wherein the catalyst is boric anhydride. 
     
     
       14. The process as claimed in claim 1, wherein the catalyst is boric acid. 
     
     
       15. The process as claimed in claim 1, wherein R has from 1 to 4 carbon atoms. 
     
     
       16. The process as claimed in claim 1, wherein R' has from 1 to 4 carbon atoms.